Multivapor petroleum refining and apparatus thereof



Dec. 14, l

M. G- HUNTINGTON MULTIVAPOR PETROLEUM REFINING AND APPARATUS THEREOFFiled 001'.- l, 1962 3 Sheets-Sheet 1 GROUND SKIP TO DISCHARGE LOCK 7 ena ge Q a COKE TRANSF FLUE GAS To LET l MEASURING BIN RECEIVE CHARGINGLOCK 5 CO2 LOCK DOWN STACK e VENT DESULFURIZ ED 0 PRESSURE PRODUCTGASOLINE A 4 a DISTILLATE a SECONDARY RETURNED To SHIP UNSATURATEDE QR oPIPEUNE SYSTEM FEEDEU B GAS To R H9 H7 GYRATORY SHELF/ K KNOCKOUT DRUMFILC IJ In PREHEI-gL I j g E 2 2 n. g a. p g 4 KNggfiaUT B Q SEPARATINGswam 0 3000 F Tyne B3 HEATING OF coKE 82 BY ITs PARTIAL L MECHANICAL ICOMBUSTION A ETHANE CLEAN our cow 4 BUEANE REFLUX- s w sEPARATIoN E ESHELF g g ETHYLENE 2 I2I 8 4| 5% ;.1 J E O HEAVY PRODUCT g g COOLER EETHYLENE 97 5* 2 GASOLINE 10 NSN 6 =A CRUDE on. 400F REFORMED VAPQL FROMSHIP QR SATURATED 5% REFORMER PIPELINE GASES T0 E /95 m n2 ggf igg I 5?46 36 I SCRUBBER QUENCH 58 as SURGE a ABSORBER VAPOR Nal TANK PRIMARY ZC84 D TOPHNG CRUDE OIL m 1 EE j 59 2Q 40 'HRT T a HEAVY Rzmcu-ik j V gTHERMAL v7/\ VAPOR No.2 V 19 0% CRACKING m 60 E; a 7 66 62 J63 37 08 I:E I I SET-*3EI I 4 CONTACT 94 RECYCLED 3 COKING BOTTOMS COLD 42k 1REFLUX g ki 74 PURGE 2 76 ifl 2 92 i am $55 9 QUENCHING A 20 LOCK 24 52R 5 STREAM x VENT m- 5 4 8| &1" I- c: 2s 0 5 5 Li- PRESSURE 2 3g: CHANGEI g o E SOLIDS-FREE TRANSFER LOCK 23 6 g HEAVY PRODUCT SURGE BINJ EDISTILLATE D' C: 82 ARIA ARTIAL COMB. P o J'HYDROGEN f HEAVY BOTTOM COKEHEATING 2 ZONE 32 RECYCLE WITH 73 I22 23 I24 ENTRAINED souos "-32%" H2+Cj V 77 METHANE CRACKING AND ,5 CH4 'A'Egfl'fg 0 INVENTOR. HYDROGENHEATNG ZONE 54 ggg em MORGAN G. HUNTINGTON a ABSOR FINAL COKE JVJQ y M IQ DISCHARGE o H a a, M760 ,han, LOCK CO2 FROM RECEIVER 35 0 FOR LOCKPRESSURING ACETYLENE ATTORNEX'SZ Dec. 14, 1965 M. G. HUNTINGTON3,223,616

MULTIVAPOR PETROLEUM REFINING AND APPARATUS THEREOF Filed Oct. 1, 1962 3Sheets-Sheet 2 lMPlNGlNG RlNG \7;

SUPPORTING SPIDER ETHANE, BUTANE,

HOT ANNULAR PROPANE, EG., IN

CASCADE ETHYLENE, PROPYLENE,

BUTADIENE our REFORMED STREAM QUENCHING T R 9? REFORMING I I08 sTREAM *1REFRACTORY LlNlNG I;

QUENCHING I ||2 00E- OE 2 40 REFORMING 5 i M STREAM *2 H0 :R

T 1 F ou NCHING i E Q FIG. 20

f HYDROGEN STRIPPING AND 95 REFORMING SECTION SEE FIG. 2b

INVENTOR.

MORGAN G. HUNTINGTON ATTORNEYS.

Dec. 14, 1

Filed 001;. 1, 1962 M. G. HUNTINGTON MULTIVAPOR PETROLEUM REFINING ANDAPPARATUS THEREOF 3 Sheets-Sheet 5 PURGE HYDROGEN FIG. 2b

DISTILLATION, CRACKING AND CONTACT COKING SECTION INVENTOR.

MORGAN G. HUNTINGTON 21, z/wbzz 2w, wm

ATTORNEYI United States Patent MULTIVAPOR PETROLEUM REFINING ANDAPPARATUS THEREOF Morgan G. Huntington, Washington, D.C., assignor toHuntington Oil Refining Company, a corporation of Nevada Filed Oct. 1,1962, Ser. No. 227,217 15 Claims. (Cl. 20889) This application is acontinuation-in-part of my copending application Serial No. 199,867(series of 1960) filed June 4, 1962, now abandoned.

This invention relates to upgrading of whole and reduced crude oils bydistillation in order to effect desalting and demineralizing and toeliminate high boiling residua, and to remove as their hydrides, sulphurand any oxygen and nitrogen that may be present.

This process also relates to continuous multivapor distillation of thewhole crude oil, vapor phase cracking of selected heavier fractions,contact coking of residua and vapor phase catalytic desulphurization andstabilization of the product oils and gases by hydrogenation and/or byrapid quenching.

This invention particularly relates to the spraying of whole and/orreduced crude oils into an incandescent cascade of crushed, carbonaceousand inert material which is sufficient in heat content to cause thedistillation of the lighter fractions, the precisely controlled vaporphase thermal cracking of heavier fractions and the contact coking ofresidua.

This invention also provides for direct catalytic stabilization of theproduct oils by hydrogenation followed by the reforming and rapidquenching of selected vapor streams so that, when desirable, thereconstituted, upgraded product can consist wholly of gasoline of goodoctane number and that any fraction of the distillate which is heavierthan gasoline, can, when required, consist entirely of high valuecomponents such as jet and diesel fuel.

This invention also provides for the coincidental decomposition ofselected recycled fractions such as paraffins to olefines and acetylenenaphthenes to aromatics, etc., performed by the very brief contactingwith incandescent coke followed by rapid quenching with hydrogen and/ orhydrocarbon vapors and/ or water.

This invention contemplates eliminating the several separate basicrefinery functions, and combines them into a single continuous system inwhich heating, topping, distillation, desalting, demineralizing,cracking, coking, desulphurizing, stabilizing of the total distillate byhydrogenation, reforming, decomposing of paraffins to olefines,acetylenes, aromatics and other unsaturates and fractionating areperformed as a continuous process and without the use of suchtroublesome conventional equipment as pipestills and coking drums.

Throughout the world, many high sulphur petroleums of low A.P.I. gravityhave little or no market value because the yield of gasoline therefromis poor and because the cost of refining such oils in conventionalplants is excessive when compared to higher quality petroleums. Thisinvention provides an incomparably low-cost means of upgrading thoseheavy high-sulphur petroleum crude and residuals which are not readilysalable. This invention provides for the refining of such oils intopremium products such as gasoline, jet fuel, diesel fuel and furnacedistillate fuel and eliminates entirely the necessity of marketingresidual oils. Although particularly applicable to low grade oil, theinvention, of course, is not limited thereto. This system also obviatesthe necessity of installing expensive apparatus for the manufacture ofpetrochemicals and other special products in order to recoup losses frominadvertently produced side streams.

ice

The thermal cracking of large hydrocarbon molecules into smaller andlower boiling point compounds, is fundamental to the refining ofpetroleum. Unfortunately, while the cracking of large paraffin moleculesinto desirable smaller molecules is readily accomplished, there are anumber of undesirable side reactions which complicate the usual process.Chief among these undesirable side reactions are the formation of heavypolymers and of light permanent gases. Thus, cracking is normally aprocess of both decomposition and polymerization. However, if the timeof residence at cracking temperature can be made very short,decomposition processes predominate and polymerization is minimized andthe resulting product exhibits a narrower and more uniform range ofmolecular weights. It is an object of this invention to provide a uniquesystem which the residence time at cracking temperature can becontrolled and made short as desired.

Known sophisticated cracking processes aim at producing a maximumpercentage of compounds in the molecular weight range of (gasoline) anda minimum of both light gases and heavy polymerized compounds. Mostimprovements in known cracking processes incorporate some means forcontrolling the time at which the feedstock is subjected to crackingtemperatures. Many processes which cannot achieve ultra-short residencetimes at very high temperatures, must include a catalyst which favorsthe production of a preponderance of desirable molecules and adsorbswhatever heavy polymer is formed. At very high vapor phase crackingtemperatures, that is, above 1200 F., the rate of decomposition is rapid(doubling once for every increase of about 3070 F.) and the time ofretention at higher temperatures, for optimum gasoline yield, mustnecessarily be measured in tenths or even hundreds of a second.Furthermore, the effect of specific cracking catalysts becomes less andless important as the temperature is raised and the residence time isshortened. This invention provides a unique arrangement for crackingpetroleum without the necessity of catalysts in the cracking vessel andin which the petroleum is directly contacted with a very hot solidmaterial for a controlled and preferably very short residence time.

The refining of high-sulphur and/or low-gravity crude petroleums aspresently practiced constitutes a cumbersome, costly, unprofitableprocess incorporating a sequence of compromise functions dictated bychanging market conditions and enormously complicated by the economicnecessity of converting into salable products various incidental sidestreams of unsaturated and complex hydrocarbons which are inadvertentlyproduced by the conventional refining system.

Moreover, in the United States, today, the combustion of sulphurouspetroleum products results in the very serious pollution of theatmosphere. While modern refining practices largely remove sulphur fromgasoline and the lighter fuel oils, the sulphur is usually concentratedin the residua which are eventually burned. The present state of the artof petroleum refining permits to be dumped into the atmosphere each year3,000,000 to 4,000,000 tons of sulphur in various chemical combinations,some of which are highly toxic to human beings and all of which causeeye irritation, damage to plants and very serious metallic corrosion ofexposed structures. It is an object of this invention to eliminatepractically all of the sulphur from the distillate and cracked productsbefore fractionation into the final products and recycle stock. Becauseof the relative simplicity afforded by this system for the controlleddecomposition of parafiins to olefines and of naphthenes to aromatics,desulfurization of the primary vapor streams can be complete andperformed without regard to the saturation of whatever olefines andaromatics which are initially formed.

It is a further object of this invention to provide a unique petroleumrefining scheme in which no residual oil is produced, thus allowing theproduction of high grade gasoline from low grade crudes and eliminatingthe necessity for marketing heavy residual oils with a high sulphurcontent. Since no residual oils are generated by the process a greateryield of high value products is produced and the overall profitabilityof petroleum refining is substantially increased.

The multivapor petrofiner of this invention incoporates heating crushedcarbonaceous material to incandescence, by its partial combustion tocarbon dioxide, with or without added inert materials. For example, thecarbonaceous material may be coke or petroleum coke produced by theprocess, with or without added amounts of natural or synthetic crackingcatalysts, or additional inert solids. Alternatingly, the solid materialmay be carbon coated inert catalysts and the carbon may be burned oif bythe combustion to a heated clean catalytic solid. The in vention furthercomprises forming a continuous cascade of the hot, carbonaceous materialin sufiicient amount to provide adequate sensible heat content for theseveral purposes of:

'(1) Complete distillation by a snowflake on a hot stove method;

(2) Vapor phase cracking of the heavier fractions;

(3) Contact coking of residua;

(4) Decomposition (thermal reforming) of parafiins to olefines andnaphthenes to aromatics;

(5) High temperature cracking processes (15002000 F.) such as theproduction of ethylene, propylene, butadiene, etc.

This invention further contemplates the formation of a cascading curtainof the initially incandescent solid material within the containingVessel and the spraying of whole and reduced crude oils and recycledlight and/or heavy oils and vapor and gases onto the cascading curtainof material at one, two, or more horizons.

This invention also incorporates provision for the metered withdrawal ofa plurality of vapors at several successive horizons of the annularcarbonaceous cascade so that the first vapor will consist of thelightest fractions, the intermediate vapors will be comprised of theheavier fractions with their cracked products and the lower vapors willconsist of the products resulting from the final contact coking ofresidua and their vapor phase cracked products. The inventionparticularly provides for the accurate control of the degree of vaporphase thermal cracking of any fraction by varying the time of contactwith the source of heat through controlled venting and withdrawal. Thus,no fraction need be over-cracked, nor must any heavy fraction bewithdrawn without suflicient thermal treatment.

This invention also provides for the very rapid removal andstabilization of cracked products in order to minimize polymerizationand thermal decomposition. This is accomplished either by rapidquenching and/ or by superheatinge-ach effiuent stream by admixing veryhot hydrogen for superheating so that the temperature of each vaporstream is raised well above the initial dew point of its heaviestcomponent and then promptly conducting the vapor stream entrained in thethermal carrier over a catalyst in order to assure that no unwantedreactive olefines are produced in the system and that all gases and alldistillates are rendered unreactive and stable by vapor phase catalytichydrogenation coincidental with the removal as hydrides of any oxygen,nitrogen and sulphur which may be present. It follows, therefore, thatnot even recycled stock to the incandescent annular cascade willcontain-polymerizable compounds or alkyl reactive group In the samemultivapor petrolfiner system and concurrently with the multifunctionalprocessing of the feedstock crude oils, light parafi'ins and naphthenes(some of which are formed during catalytic desulphurization) can bedecomposed (thermally reformed) to olefines and to aromatics. Thus, thegasoline produced can, when desirable, consist chiefly of olefines andaromatics. Furthermore, jet fuels can be routinely produced with anyspecified aromatic content when incorporating solvent extraction orhydrogenation to naphthenes.

Further, the multivapor petrofiner can be concurrently used for varioushigh tempearture decomposition reactions such as the cracking of butaneat temperatures in the order of 2000 F. for the optimum yield ofethylene.

This invention further provides that some of the permanent gasesgenerated by the process, such as methane, will be thermally cracked tohydrogen and elemental carbon and simultaneously heated in a separateportion of the same apparatus or a similar separate apparatus. Thus,there need be no outside source of hydrogen nor of fuel. The crackedmethane stream can be quenched by water to retain and separateacetylene.

This invention also provides for hydrogen, generated by thermallycracking the necessary amount of permanent gases and heated above 2000F., to be tempered by cooler hydrogen and admitted to multivapordraw-off ducts to supply a suitable partial pressure of hydrogen andadjust each vapor stream to optimum temperature for catalytic vaporphase desulphurization and for the saturation of polymerizablemolecules.

This invention additionally provides for the thermal reforming ofselected vapor streams subsequent to desulfurization according tospecifications desired by prospective purchasers.

It is also incorporated in this invention that whatever nonvolatilessuch as salt, metallic compounds and residual fixed carbon remain withthe solid fuel cascade and that the upgraded liquid distillate productwill thereby be desalted, demineralized, and upgraded to contain onlyreadily salable components.

Severe hydrodesulphurization can be performed upon the primary vaporstreams produced in this invention without the regard necessary inconventional systems for the coincidental saturation of olefines andaromatics because this invention provides a convenient and economicmeans of thermally reforming any number of recycled or separatelyintroduced side streams by introducing them into a cascade of very hotsolid carbonaceous materials. Moreover, the vapor streams may bedeliberately saturated by catalytic hydrogenation so that thermalreforming may be uniformly performed to yield a minimum of permanentgases and a maximum of desirable liquid hydrocarbons.

All of the heat for the system is provided by the partial combustion ofanthracite coal, coke, petroleum coke or other suitable solidhydrocarbonaceous or carbon coated inert materials to carbon dioxide inoxygen. Hydrogen for the system is furnished by thermal decomposition ofreformed fractions and, when necessary, is supplemented by the thermalcracking of methane generated in vapor phase cracking and hydrogenstripping operations. Thermal control of vapor streams subjected tocatalytic desulphurization is eifected by the admixing of hydrogen atsuitable temperatures.

The distillation of the liquid oil feedstock in this inventionincorporates a snowflake on a hot stove concept, so termed because ofthe similarity of snowflakes dropping on a very hot stove andimmediately vaporizing to the oil feedstock droplets contacting the veryhot incandescent cascade and immediately vaporizing. Further, the vaporsproduced in the distillation function may be instantly removed from theheat source, quenched by hydrogen and/or light hydrocarbon vapors andmaintamed in a vapor phase by reducing the partial pressure of theheavier constituents in order that complete vapor phase desulphurizationand saturation may be promptly performed on each product stream.

This invention is entitled The Multivapor Petrofiner because a pluralityof hydrocarbon vapors may be continuously withdrawn from the system atmeasured and controlled rates. The quality of the several vapors can beaccurately controlled so that for example, one or more vapors may becomprised entirely of straight run distillates or one or more vapors mayconsist chiefly of vapor phase cracked products of any higher boilingrange distillate. Moreover, the multivapor system of this inventionincorporates in a single continuous operation such usually complexpetroleum refinery functions as 1) topping off straight run gasoline,(2) distilling and removing as a separate vapor any desired boilingrange fraction, (3) coking of residua, (4) vapor phase cracking of anyhigher boiling range fraction into products of predictable molecularweight, (5) decom- .posing selected recycled streams of C C C etc.,paraffins to olefines and decomposing naphthenes to aromatics, and (6)high temperature (in the order of 2000" F.) cracking reactions, such asthe production of ethylene, propylene, butadiene, etc. from butane,propane and ethane.

As is explained here below, selected vaporized distillate fractions maybe subject to high temperature thermal and/or catalytic treatment duringaccurately controlled periods of time as short as a few hundredths ofone second when required. Furthermore, two or more such vapor streamscan be introduced into the same vessel and subjected to separate andaccurately controlled thermal treatment.

It should be pointed out here that no other device in the petroleumindustry removes more than a single composite vapor from any catalyticor thermal cracking operation While this invention can remove from thesame vessel simultaneously many separate vapor streams which have beensubjected to separate thermal treatment. Therefore, rather thanover-treat the more easily cracked components while under treating themore resistant frac tions, as is the case in all other cracking andcoking systems, this multivapor method can accurately control thetimetemperature history of each separate efliuent stream.

This invention replaces the multitude of pipestills and heated coils,heat exchangers, reformers, crude oil toppers, coking drums, crackingstills, catalytic crackers, etc., which are standard equipment in themodern refinery.

Other objects of the invention will be pointed out in the followingdescription and claims and illustrated in the accompanying drawingswhich disclose by way of example the principle of the invention and thebest mode which has been contemplated of applying that principle.

In the drawings:

FIGURE 1 is a schematic illustration of an integrated vertical retortvessel showing the annular cascade of solids, the mechanics of theirpartial combustion to carbon dioxide, and the manner of transferringheat from the hot solids to the oils, vapors, gases under treatment, andalso includes a flow diagram of the various fluid streams of the system.

FIGURE 2a is a schematic illustration of the high temperature butanecracking and ethylene production section and the thermal reformingsections which lie below the system feeder shelf.

FIGURE 21] is a schematic drawing of that section of the vertical retortvessel directly below that shown in FIGURE 2a in which are performed thefunctions of topping the oil under treatment, distilling and selectivelycracking heavier fractions, coking the residua and removing a pluralityof separate vapors therefrom.

Basically, when operated as an upgrader of off-grade whole and reducedcrude oil feedstock, this invention includes an essentially once-throughprocess whereby the 6 crude oil is desalted and demineralized bydistillation, the residual content is eliminated by contact coking, andwherein all products are freed of nitrogen, sulfur, and oxygen; andreactive olefines are saturated and rendered stable by catalytichydrogenation.

The vertical retort shown in FIGURE 1 receives solids, liquids andvapors and discharges solids and vapors. FIGURE 1 includes the flowsheet diagram of both an annular cascade of solid carbonaceous materialsand the fluid flow of the process. The term solid carbonaceous materialsand the like used herein also includes any accompanying inert orcatalytic materials, or carbon coated refractory catalytic materials.

The apparatus of the subject invention is, except for the sections shownin detail in FIGURES 2a and 2b, a unique combination of constructionsshown and described in detail in my prior copending applications SerialNo. 17,293, now Patent 3,083,471; Serial No. 41,679, now Patent3,107,985; and Serial No. 186,920. More specifically, the apparatusincludes a relatively large vertical pressure vessel having a number ofbins such as bins 1, 3, 16, 23, and 35, which may be closed by suitablebell valves 2, 4, 20, 21, 22, etc., as shown schematically in FIGURE 1.Two adjacent bins, such as 1, 3 and their associated bell valves mayconstitute a pressure lock. Suitable valved inlets and outlets, such asvalved inlet 5 and valved outlet 6 in bin 3 are provided for each of thepressure locks as may be necessary.

Within the pressure vessel 50 there are a number of gyratory shelves,which may be solid material feeders and/or gas isolating separators. Seegyratory shelves 8, 13, 14, 30, and 32. Each of these gyratory feedershelves may carry solid materials in a sufficient density and depththereon to effectively prevent gas diffusion from one side thereof tothe other to thereby create gas isolated sections within the pressurevessel 50. The gymtory shelf mechanism also feeds the solid materials byproviding a controlled annular cascade of solid materials over theperiphery thereof, and the structure and operation of such shelves isdescribed in detail in my copending application Serial No. 17,293, filedMarch 24, 1960, now Patent 3,083,471. Reference may be had to thiscopending application for the mechanical details of the gyratory shelfmechanisms, and the like.

Also within pressure vessel 50 there are two partial combustion chambers12 and 31 for the heating of solid carbonaceous material, such as coke,by its partial combustion to carbon dioxide. Dual oxygen injection inletand a C0 offtake are provided for each partial combustion chamber.Rather than burden the disclosure with a detailed explanation of theoperation of these partial combustion chambers, reference may be had tomy copending application Serial No. 186,920, filed April 5, 1962, for adetailed disclosure of the construction and the method of operation ofpartial combustion chambers 12 and 31.

Also contained within the pressure vessel 50 is a methane cracking andhydrogen heating zone 33 which is similar to a zone of this typedescribed in detail in my copending application Serial No. 41,679, filedJuly 8, 1960, now Patent 3,107,985, and reference may be had to thiscopending application for the construction and op eration of methanecracking and hydrogen heating in great detail.

In addition to the pressure vessel 50 and the adjuncts of pressureadmitting and discharging valved lines for the pressure locks describedabove, there are various metered oxygen intakes for the partialcombustion zones as described in my aforesaid application, as well as COofftakes for the partial combustion zones together with mechanicalcleanouts and knockout drums. There further is provided means forintroducing varied fluids into the system as will be described inconnection with the method.

The principal novel apparatus features of this invention resides in ahydrocarbon stripping and reforming section 19, illustrated in detail inFIGURE 2a; and a distillation, cracking and contact coking section 15,shown in detail in FIGURE 2b. The distillation, cracking and contactcoking section 15 has a conduit 18 with a metered valve 91 therein forcontrolling the admission of crude oil and recycled oil into the systemfrom a spray head 17 onto a deflecting cone baffle 40. The distillationcracking and contact coking section 15 is directly below the hydrocarbonstripping and reforming section 19, although by suitable controls thereis only minimal intermixture of the gases therein.

Within the distillation section 15 there are a number of verticallyspaced vapor offtakes. The first vapor offtake 44 is above the crude oilinlet spray head 17 and includes a deep radiant shielding skirt 86 forshielding the spray head from the radiant heat of the annular cascade ofhot solids. Below the spray head 17 are a plurality of additional vaporofftakes. While any number of such offtakes may be employed, there areillustrated at 41, 42, and 48. Vapor oiftake 48 may have a shortenedofftake cone, while vapor offtakes 41 and 42 may have deep skirts 87 and88 to confine and constrict the annular cascade of hot solids. The corebaffle 43 is to prevent boiling up of the solid materials and it spreadsthe purge hydrogen stream around its edges and upward into contact withthe falling cascade of hot solids for the purpose of purging vapors fromthe spent fixed carbon of the solids. Below the last vapor oiftake,there is a core baflie 43 which in turn is positioned above a purgehydrogen inlet 74.

Each of the vapor offtakes is connected to a knockout drum and tarprecipitator schematically illustrated as drums 57, 61, 66 and 67, andmechanically cleared offtake duct leads from each offtake cone to theassociated knockout drum. Behind each knockout drum there is acontrollable positive displacement valved metering device such as valvedmetering devices 46, 62, 67, and 71.

In the hydrogen stripping and reforming section of FIGURE 2a there are aplurality of spray cone inlets,

103, 108, and 110 connected to metered inlet lines. Immediately belowthe inlets are skirted cone metered outlets 105, 109 and 111. Separatedquench inlets 97, 96 and 95 are also provided as shown.

Referring again to FIGURE 1, the flow diagram schematically showsadditional elements which are well known in the petroleum refining art.These elements include desulphurizing and saturating catalyst chambers47 and 64, a primary fractionator 60, primary condenser 59, a secondaryfractionator 114, a secondary condenser 117, and various lines, pumps,coolers, etc. as normally employed with such apparatus, but connected asshown in FIGURE 1.

The operation of this process may be described as follows: Solidcarbonaceous material, preferably coke resulting from the process, iscrushed so that the terminal velocity of the freely falling particles inthe gases encountered will, for example, be between and 30 feet persecond. Occasionally mixed with the ground carbonaceous material may belarger pellets of hard coke and/or fragments of refractory materialadded for the purpose of breaking and scouring scabs and accretions fromthe internal walls of the retort. For certain purposes, catalyticmaterial may also be added to the crushed carbonaceous material.

The charge material is elevated by skips or by some other suitable meansand is dumped into measuring bin 1. Through the operation of bell valve2, the solid charged material is admitted into the charging lock 3.Charging lock 3 is cyclically pressurized and depressurized with carbondioxide from flue gas receiver 7, regulated by inlet valve 5 and ventvalve 6. By further cyclic operation of the charging lock, and byclosing bell valve-2, pressurizing lock 3 and subsequently opening bellvalve 4, the contents are dumped upon a gyratory system feeder shelf 8.

Gyratory feeder shelf 8 provides a uniform annular cascade of solid fuelwhich, when dropping freely into a solids preheat chamber 10, will flowconcurrently with hot carbon dioxide admitted through duct 11, whichoriginates as a product of combustion from the partial combustionchamber 12.

Carbon dioxide used for preheating of the carbonaceous charge iswithdrawn at dust cone 52 from chamber 12. The carbon dioxide from cone52 is conducted through knockout drum 53 and cooler 26 to flue gasreceiver 7. This gas may be used to pressurize charging lock 3. Thecarbon dioxide from chamber 12 is also treated in a knockout drum 9 andmay then be recycled to the coke preheating zone 10 through duct 11.

At the lower end of the preheating zone 10, the preheated chargematerial forms a deep separating bed whose depth is controlled by thevariable amplitude and gyrating rate of shelf 13 reacting a gamma raydensity sensing apparatus or other suitable level control device. Bycontrolling the system so that there is practically no pressuredifferential across bed 13, the deep bed of preheated solids effectivelyprevents the very hot carbon dioxide in partial combustion zone 12 fromflowing countercurrently against the freely falling carbonaceousmaterial which occurence would result in the undesirable formation ofcarbon monoxide. Causing the very hot carbon dioxide to flowconcurrently with the carbonaceous material in preheating zone 10insures against the overheating of the carbonaceous material andpractically eliminates the formation of carbon monoxide from the carbondioxide and carbon.

The process heating of coke or other carbonaceous material by itspartial combustion to carbon dioxide in chamber 12 by the dual admissionof oxygen is, as mentioned before, described in detail in my copendingapplication Serial No. 186,920, filed April 12, 1962..

The charge solids heated by its partial combustion to a temperature inthe order of 1500 F. to 2500 F., or even better, according to therequirement of the process, accumulates upon separating shelf 14 to formanother deep separating bed suitably controlled in depth by a densitysensing device, and this bed serves to separate the zone of oxide gasesfrom the zone of hydrocarbon vapors. Because the oxygen is metered intozone 12 and the carbon dioxide metered out and because crude oil andvapors are likewise metered in and out of the zones 19 and 15 on theother side of shelf 14 the deep separating bed on gyrating shelf 14serves chiefly to prevent diffusion of oxide gases into the hydrocarbonstripping and reforming zone 19. That is, the various metering deviceson the inlets and outlets of each zone insure against any substantiallypressure differential existing across separating shelf 14.

The gyratory shelf 14 operates in the manner described in my aforesaidcopending application Serial No. 17,293, now Patent 3,083,471, andprovides a uniform annular cascade of solid incandescent material whichfalls freely through hydrocarbon stripping and reforming zone 19. Forexample, ground freely falling coke may enter the hyrocarbon strippingand reforming zone 19 at a temperature as high as 2500 F. (unless it isintentionally cooled by adding solid material at a lower temperature orby reducing the rate of combustion oxygen flow in the partial combustionzone 12). The coke continues to fall through the distillation crackingand contacting coking zone 15, and finally reaches surge bin at atemperature in the order of 1300 F. after having supplied the sensibleheat for stripping and reforming of hydrocarbon gases and for thedistillation, vapor phase cracking and contact coking of the crude oiland recycled heavy bottoms which liquids are admitted into contact withthe coke through spray head 17 duct 18, measured by meter 91. Theannular cascade of very hot solid materials therefore provides the heatto accomplish the stripping, reforming, distillation, vapor phasecracking, and contact coking of the various fee-d products which mayinclude vapors, gases and liquids. The liquids will immediately bevaporized upon contacting the hot annular cascade and then may betreated and withdrawn as vapors. The hydrocarbon stripping and reformingzone 19 land the lower contiguous distillation, cracking and contactcoking zone 15, will further be described in detail below.

The crushed coke cascade may be increased in amount and capacity overthat of entering the system through charging lock 3 by recirculatingcoke between surge bin 90 and separating feeder shelf 13 as is explainedin my copending application Serial No. 266,255, filed March 19, 1963.Such apparatus for recirculation of the solid carbonaceous materials isnot shown herein for the sake of simplicity.

The material in surge bin 90 is retained by turnip valve 20 in order toallow the gas tight closing of turnip valves 21 and 22 and pressurechange coke transfer lock 23. Coke transfer lock is pressurized bycarbon dioxide raised to a suitable pressure by compressor 24pressurizing receiver 25. The source of carbon dioxide may be from thecombustion product from partial combustion zone 12 which is cooled andstored in flue gas receiver 7.

By the suitable operation of turnip valves 20, 21 and 22 and coketransfer lock pressurizing valves 28 and 29, coke is admitted to surgebin 27 at a somewhat higher pressure than exists in the upper part ofthe system comprised of zones 10, 12, 15 and 19. Gyratory shelf 30 nowbecomes the system feeder for the methane cracking system and the hotsolid material, which now contains whatever salts and fixed carbon whichmay have been extracted from the treated crude petroleum, falls as anannular cascade into the secondary partial combustion zone 31 where thesolids are raised above 2500 F. by partial combustion of carbon tocarbon dioxide. The method of partial combustion in zone 31 may also becarried out in a manner similar to that in zone 12, and as fullydescribed in my copending application Serial No. 186,920.

The reheated high temperature coke falls upon gyratory shelf 32, theaccumulation of which forms a deep separating bed between the secondarypartial combustion zone 31 and the methane cracking and hydrogen heatingzone 33. Gyratory shelf 32 again feeds the incandescent coke in anevenly distributed annular cascade in order to optimize heat transferbetween gases and solids in zone 33. The annular cascade of reheatedground solid material, falling freely through zone 33, furnishes thesensible heat for heating of methane and to accomplish its thermaldecomposition to hydrogen and carbon dioxide. Methane recycled from thesystem is introduced through metered inlet 54, contacts the falling cokeat 2500 F. or above, and is cnacked into hydrogen and carbon. Bothhydrogen and carbon black which leave the system above 2000 F. througholftake 55 above core baflle 56 and the hot hydrogen may be used tofurnish heat for the superheating of vapor streams before catalysis inorder that no liquid mist remains to coat the catalyst.

The cracked product stream in line 73 may be utilized for the productionof acetylene by admitting the stream through valve 122 to a quencher123, followed by a compressor 124 and adsorber 125; thereby extractingnearly pure acetylene by water absorption as is well known in the art.

Having furnished the sensible heat for methane cracking and the heatingof the cracked products, the annular solid material cascade may stillcontain substantial heat which may be recovered by various means. Forexample, methane and recycled hydrogen from the scrubber and absorbermay be introduced into the cascade above bin 34 (not shown) and the cokewill then reach the discharge surge bin 34 at a temperature in the orderof 300 or 400 F. The spent solids containing whatever salt, fixed carbonand other solids removed from a heavy oil undergoing treatment, is thendischarged from the system by the suitable operation of discharge lock35 being alternately pressurized and depressurized with carbon dioxidewhich is a flue gas from the primary combustion chamber.

Since the solids are continuously increasing in amount, some of them maybe recycled and part rejected (by conventional apparatus, not shown),thereby allowing for the continuous removal of salt and othernonvolatile and noncombustible solids.

The flow path of the cascading solids has been described together withthe fiow path of the heating gases and vapors. The flow path of thedistilled and thermally cracked vapors will now be described inconnection with FIGURES l and 2 (2a and 2b).

Referring first to FIGURE 2b, crude oil and recycle oil at about 200 F.is admitted through duct 18, metered by meter 91 and sprayed against thehot annular cascade of incandescent solids through spray head 17 afterbeing deflected off cone 40. It is also contemplated that solid organicmatter such asphaltenes precipitated from petroleum and/or pulverizedcoal can be entrained in the recycle and crude oil stream and sprayedagainst the hot annular cascade to eflect carbonization and partialconversion to useful liquids.

The vapors indicated by arrows 39 are those which have the lowestboiling range, e.g. about 200 F., and therefore, distill first andconstitute the familiar refinery function of topping. The vapors fromthe initial distillation immediately leave the source of heat in thezone 15 and are subject to no further thermal treatment, but isdesulphurized after being brought to temperature by the admixing of hothydrogen. The vapors pass from the first vapor offtake 44 throughmechanically cleared offtake duct 45, knockout drum and tar precipitator57 and are metered through positive displacement meter 46 and thence toline 58. For desulphurzation of this vapor it is passed through conduit63 to desulphurizing catalyst chamber 64 and catalytically hydrogentatedin a manner similar to the other vapor streams as will be described. Itwill be noted that the vapors first produced are those of low molecularweight and hence require no thermal cracking to yield molecules in thegasoline Weight range and may possibly therefore be immediately removedfrom the system, desulphurization is not necessary.

The crude oil feedstock is progressively and very rapidly heated as itfalls through the distillation and cracking zone 15 in contact with theannular solids cascade. The liquid absorbs heat very rapidly anddistills off vapor of progressively heavier and heavier molecularweight. Such heavier vapors can be withdrawn directly into subsequentvapor otftake cones 48, 41 and 42 or, through proper metering, can beforced to pass concurrently with the very hot annular cascade of groundsolids and thereby be subjected to any desired degree of thermalcracking. For example, whatever vapor is boiled off below spray bafflecone 40 and olftake cone 48 can, by suitable metering of the variousvapor outlets, be forced to flow concurrently with the descending fuelcascade and be drawn off through oiftake cone 41, or, if more extensivethermal treatment is required, the vapors can be forced to remain evenlonger with the hot solid material cascade and be metered from thecracking zone, e.g. through cone 42.

As a further example, all of the heavier molecular weight vapors beyondthe very lightest can be made to suffer thermal alteration by merelyclosing all outlet valves on the second, third, and fourth vaporolftakes, offtakes 48, 41, and 42 thus forcing all of the vapors to passcounterconcurrently up against the descending hot solids cascade to bewithdrawn through cone 44. In this manner, for example, the lighter andlowest boiling hydrocarbons would be subject to no thermal treatmentother than simple distillation, while the heaviest and highest boilingfractions could be subjected to the 'most severe thermal cracking.

Likewise, the medium boiling range components would receive onlymoderate thermal treatment.

Through incorporating a suitable number of such vapor offtakes and byvarying the rate of metering, a wide variety of cracked product can bemade by this very efficient system. At the same time, the crude oil hascompletely changed its form and the product is solely that of adistillate with varying amounts of cracked molecules with an upperboiling range to suit any refinery customers specifications. It is,therefore, evident that the particular number of olftakes shown is byway of non-limiting example only.

A mechanically cleared oiftake duct from cone 48 directs the vaporthrough a knockout drum and tar precipitator 61 and then through acontrolled or valved metering device 62 into line 63. Next, the vaporand hot hydrogen, which is admitted through line 76, is passed into afirst desulphurizing and saturating catalyst chamber 64 (chamber No. 1),for catalytic hydrogenation of the vapor to remove and prevent theformation of chemically troublesome compounds. Thus, organic compoundswhich contain functional groups of oxygen, nitrogen, and sulphur arecompletely destroyed. Also, this treatment avoids the polymerization ofreactive unsaturated hydrocarbons into undesirable large molecules whichform gums and tars. The output from the catalyst chamber 64 is line 65which leads into primary fractionator 60.

The vapor from the third offtake, olftake cone 41 also goes through amechanically cleared offtake flue into a knockout drum and tarprecipitator 66 and then through a controlled valved metering device 67to a line 68. The vapor is then directed to another desulphurizing andsaturating catalyst chamber 47 (No. 2) after being combined with astream of hot hydrogen admitted through line 75. The function of thisdesulphurizing and reforming catalyst chamber is the same as catalystchamber No. 1, but different catalyst chambers may be tailored todifferent results, e.g. to produce different specific products. Theofftake then passes through line 69 to primary fractionator 60.

From the fourth vapor offtake 42, the thermally cracked vapor can passthrough mechanically cleared offtake duct, a knockout and tarprecipitator 70, and a controlled metering valve 71 into line 72. Afterbeing mixed with hot hydrogen admitted through line 76, the vapors thenpass into No. 2 desulphurizing and saturating catalyst chamber 47.

When demineralizing feedstock oils which contain volatile metalliccompounds which may distill over at cracking coking temperatures, aseparator may be included in line 72 (not shown) to confine suchmetallic volatiles into separate streams for redistillation at lowertemperatures.

Hot hydrogen and some carbon black removed from the methane cracking andhydrogen heating zone 33, through oiftake cone 55, pass through line 73and are introduced into zone through hydrogen inlet 74. Additional hothydrogen mentioned above passes through line 75 to be mixed with thevapors passing to the desulphurizing and reforming catalyst chamber 47.Hydrogen also passes through line 76 to be mixed with the vapors goinginto desulphurizing and reforming catalyst chamber 64. The hot hydrogenis thus introduced into each vapor stream so that when necessary, thetemperature of the stream is raised well above the initial dew point ofits heaviest component. The stream is then conducted promptly with thethermal carrier hydrogen over the catalyst in the chambers to insurethat no reactive olefines remain in the system and to further insurethat when required and desirable, all gases and all distillates arerendered unreactive and stable by vapor phase catalytic hydrogenation.

From the primary fractionator 60 the heavy bottoms are moved by pump 77through line 37 for recycling. The bottoms pass through a surge tank 78.Valve 79 controls the admission of the recycle bottoms into the inletconduit 38, which in turn is controlled by meter 91. The crude oil to betreated may be admitted from a ship or pipe lines through system inlet36 and is controlled by suitable valve 86 for admission into line 38 tobe injected into the system, and as mentioned above the whole or reducedcrude oil feedstock may incorporate other materials.

Cold reflux is admitted through intake 80 to the primary fractionator60, while solids-free heavy product distillate (jet fuel, diesel fuel,stove oil) passes out of the fractionator through offtake 81 and iscooled in heat exchanger 82 before removal through a product distillateline 83.

The overhead from the primary fractionator 60 goes to primary condenser59, and from condenser 59 the condensed product passes through offtake85 to be directed to a thermal reformer (not shown). The overhead fromcondenser 59 includes saturated gases which pass to a primary scrubberand absorber (not shown) through line 84. Then some of the gas from thescrubber and absorber, including the methane and other permanent gases,may be recycled through intake cone 54 for cracking of the methane sothat all of the hydrogen used is generated in the system itself and nooutside source of hydrogen is necessary.

Butane, butylene, propane, propylene, etc. can be separated from theintermediate and final product streams for the manufacture of alkyl andpolymer gasoline, which is standard practice. Surplus butane, propane,pentane, etc. can be returned to the multivapor column and subjected toprecise heating and quenching in order to produce butylene and propylenefor greater yield of alkyl and polymer gasoline.

The zones 15 and 19 may be operated at varying pressures ranging fromless than 1 to 30 or more atmospheres provided that the partial pressureof hydrogen is sufficient to allow the vaporization of desirablefractions.

For the purposes of rapid quenching of certain selected vapors in thevarious vapor takeoifs in the distillation, cracking and contact cokingzone 15, there is provided a quenching stream in line 92 with sidebranch inlets 93 and 94 for supplying quenching gas to vapor otftakes 41and 42. Distributing baflle plates 98 and 99 are provided for thequenching gas inlets 93 and 94 respectively so that the quenching gasintimately mixes with the vapors being taken off to rapidly quench thesame. The quenching gas may be hydrogen or it may be recycled lighthydrocarbon vapors.

As shown in detail, in FIGURE 2a a hydrogen stripping and reforming zone19 includes a top section providing an incomparably efficient andeconomical means for manufacturing ethylene, propylene, butadiene, etc.,from refiinery gases, while the next two lower sections provide meansfor reforming of certain liquid streams as they are recycled. Referringspecifically to the apparatus, below the feeder shelf 14 and within theannular cascade there is an inlet cone 103 connected to a metered inletline 104 for introducing ethane, butane, propane, etc., into the hotannular cascade. Below inlet cone 103 is an offtake cone 105 with arelatively deep skirt 107. The depth of the skirt 107 on the outlet coneis predetermined in accordance with the other variables of the process.The incoming gases are admixed with the hot annular cascade and may bewithdrawn through the ofitake cone 105 and metered ofltake duct 106while at the same time being quenched with the quenching gas (hydrogenor recycled ethylene) through an inlet 97 below a quench gas bafile 102.The very hot annular cascade thermally reforms or cracks the incomingproducts into ethylene, propylene, butadiene, etc., depending on theparticular incoming feed gas.

Within the same pressure vessel 50 and below the ethylene productionsection there is a reforming section which may be composed of any numberof liquid inlets and vapor offtakes. For example, through a meteredvalve inlet cone 108, C plus reforming stock from primary condenser 59may be introduced into the annular cascade and they may flow downwardlybelow the skirt of oiftake cone 109 while being reformed and then passout through a metered valve otftake. A quenching stream 96 below aquenching baffie 101 may also be provided. In the next sectionimmediately therebelow, a heavier reforming stock in the range of 200 F.to 400 F. may be introduced through a metered valve inlet cone 110 andpass around the skirt of offtake cone 111 to pass through a valvemetered oiftake duct into a reformed stream line 112. Again, a quenchinggas may be introduced through inlet 95 below a quenching gas spreaderbafiie plate 100. Thus, two or more reforming stock streams may besubjected to different thermal treatment, in the way of hydrogenstripping operation.

Of course it will be understood that the skirts of the various olftakecones may be of different lengths depending on the time of thermaltreatment desired. Also, it is to be noted that the showing in FIGURE 2ais primarily schematic and that the various supports, insulation, etc.,which of course are necessary in the very high temperature environment,have not been shown for the sake of simplicity.

The reformed vapor stream in line 112 passes to secondary fractionator114. Cold reflux may be admitted through inlet 120 into secondaryfractionator 114 and the bottoms from fractionator 114 pass out throughline 115 to be introduced into the lower portion of primary fractionator60. Heavy product gasoline may pass off the secondary fractionatorthrough line 121 and the overhead from the secondary fractionator goesto a secondary condenser 117. Light product gasoline passes out as aliquid from the secondary condenser 117. From the gas outlet ofcondenser 117, secondary unsaturated gases pass to an absorber (notshown).

As can be appreciated from the foregoing, there are a relatively largenumber of variables which can be controlled to control the variousfunctions of the system. In the cascade of solid materials; thetemperature of the cascade may becontrolled, the proportionate amount ofcarbon inerts in the cascade may be controlled, the particle size andaverage terminal velocity of the materials in the cascade may becontrolled, and the particle ratio of surface area to volume my becontrolled. In liquid phase cracking, the partial pressure of theheavier components and the system pressure, can be controlled todetermine the time required to vaporize and therefore the time at whichthe heavier components are in contact with the hot cascade. Furthermore,control of vapor phase cracking is achieved by the particular oiftakeused for drawing off the vapor and the time the vapor is allowed to stayin the hot incandescent cascade, the rate of vapor draw-off and the rateand degree of quench either by hydrogen or other permanent gases. Also,the admission of hydrogen, either hot or cold, to the product streams ina molecular ratio of 2-10 hydrogen to one of the hydrocarbon stream maybe used to control the heat capacity and to provide a wide range ofadjustments in the process.

The use of the term solid carbonaceous materials and similar terms asused in the claims for the solid material feedstock, is intended toinclude all suitable solid materials and inerts carried thereby. Forexample, the feedstock could consist of ground coke and other suitablematerial such as petroleum coke or anthracite coal and various inertsmay be incorporated therein which would also be heated up and carriedthrough the system. Further heated refractory catalysts or inerts, orcarbon coated similar materials can be used for the cascade.

The liquid petroleum feedstock could be whole or reduced crude oil whichcould be used plain or with suitable admixture not only of recycledbottoms but also of solid hydrocarbonaceous organic matter such asasphaltenes and pulverized coal entrained in the recycled stream toeffect carbonization and conversion to useful liquid molecules.

As can be seen from the foregoing, the usual separate refineryoperations are combined in a single system. Furthermore, by controllingthe metering of the various vapor offtakes, various products may beproduced to customer specification. The only input materials to thesystem need be the solid feed material, oxygen plus the feedstock crudeoil to be upgraded. The inert and heating CO gases used in the systemare produced within the system and the hydrogen used in catalytichydrogenation is also produced within the system. The residua or heavybottoms are recycled and further treated in the contact coking zone andthe resulting products may be only straight-run distillates or vaporphase cracked products. It is further noted that the different vaporstreams may be subjected to separate and accurately controlled differentthermal treatment by means of the process disclosed. In addition, hightemperature decomposition reactions as well as reforming may take placeconcurrently in the vessel. The products of feedstock oil distillationare saturated so that subsequent thermal treatment will result in a highproportion of valuable products.

I claim:

1. A method of upgrading crude oil comprising; contacting crude oil witha free falling cascade of solid carbonaceous materials at a temperaturesufficient to distill crude oil and in sufficient amount to provideadequate sensible heat for distillation of the crude oil and thermalcracking thereof, introducing said crude oil into contact with the freefalling cascade of solid carbonaceous materials during the free fallthereof, providing a hydrogen environment for said contacting,selectively withdrawing hydrocarbon vapors from a plurality of differenthorizons adjacent the point of contacting the crude oil with the cascadeso that different and mixed vapors may be withdrawn from the differenthorizons, and catalytically treating at least some of the so withdrawnhydrogen entrained vapors to saturate with respect to hydrogen and toremove organically combined oxygen, nitrogen and sulphur as respectivehydrides.

2. A method as defined in claim 1 further comprising, initially heatingthe solid carbonaceous material to the required temperature by itspartial combustion in a closed gas isolated chamber.

3. A method as defined in claim 1 wherein the contacting of the crudeoil with the cascade of solid fuels is accomplished in a closed chamber,and the catalytic treatment of the cracked crude oil vapors isaccomplished under controlled temperature conditions.

4. A method as defined in claim 3 further comprising, separating methanefrom the withdrawn and treated hydrocarbon vapors, obtaining thehydrogen for the methane environment by cracking the methane over hotsolid carbonaceous materials in a zone separate from the contacting ofthe crude oil with the solid carbonaceous materials, and recyclingselected fractions obtained by fractionating the withdrawn and treatedhydrocarbon vapors for contacting the cascade while the cascade isfalling to accomplish thermal decomposition of the fractions.

5. Petroleum refining method comprising, spraying feedstock crude oilinto an incandescent cascade of solid materials at an incandescenttemperature sufiicient to cause distillation and cracking of saidfeedstock crude oil and in an amount having sensible heat available forthe distillation and cracking while the solid material is falling withina closed chamber and in a hydrogen environment, distilling the lighterfraction of said feedstock crude oil by the contacting thereof with theincandescent cascade of solid materials and selectively and controllablythermally cracking the heavier fractions, controllably withdrawing thevarious fractions from different horizons within the closed chamber,catalytically hydrogenating at least some of the thermally crackedfractions, and further utilizing selected horizons of the cascade forhigh temperature cracking of gases and thermal decomposition andreforming of selected streams obtained from the withdrawn streams aft-erfractionation and recycled to contact the cascade.

6. A multivapor method of desalting, desulphurizing and upgradingfeedstock oils comprising, heating solid carbonaceous materials toincandescence by partial combustion to carbon dioxide in a closedvertical vessel, providing a free falling cascade of the so heatedincandescent solid carbonaceous material in the vessel in sufficientamount to provide adequate sensible heat for all subsequent thermaltreatments of feedstock oils, liquids and gases, providing a hydrogenenvironment in the closed vessel around the cascade contacting thecascade with selected gases at one horizon for thermal cracking thereof,contacting the cascade at another horizon with recycled reformingstream-s to accomplish the thermal reforming thereof, admittingfeedstock oil into the incandescent cascade falling within the vessel,distilling lighter fractions of the feedstock oil and thermally crackingheavier fractions of the feedstock oil as the oil is in contact with thehot incandescent materials, selectively and controllably withdrawing theproducts of the distillation and thermal cracking as fluid streams fromvarious horizons within the closed chamber, and catalytically treatingat least some of the thermally cracked fractions of the feedstock oilstream in an atmosphere of hydrogen.

7. A method as defined in claim 6 further comprising immediatelyquenching selected ones of the withdrawn streams and superheating eachvapor stream of the thermally cracked fractions with predominatelyhydrogen gas at a temperature above the dew point of the heaviestcomponent of each said vapor phase stream.

8. A method as defined in claim 7 wherein the catalytic treating isaccomplished by conducting the vapor stream and entrained hot hydrogenover a catalyst for vapor phase catalytic hydrogenation and coincidentalremoval of oxygen, nitrogen, and sulphur.

9. A method as defined in claim 8 wherein the feedstock oil containsrecycled bottoms and granular solid hydrocarbonaceous materials.

10. A method as defined in claim 8 wherein the hot hydrogen is obtainedby thermally cracking methane over hot solid carbonaceous materials inthe same system, and further comprising obtaining the methane for thethermal cracking to produce hydrogen from the products of distillationand the gas produced thereby without necessitating using an outsidesource of methane.

11. A method as defined in claim 10 further compris ing rapidlyquenching at least some of the cracked meth* ane stream, followed bypreforming compressing and ab sorbing operations on the quenched streamto obtain acetylene.

12. A multivapor method for oil refining comprising, heating toincandescence by partial combustion to carbon dioxide solid crushedcarbonaceous materials in a pressurized vertical vessel, feeding the soheated incandescent I solid carbonaceous materials in the vessel toprovide a free falling cascade in a gas isolated chamber, the solidmaterials being suflicient in amount to provide adequate sensible heatfor subsequent thermal treatment of feedstock oil and recycled reformingstreams, introducing crude oil into the chamber and contacting the crudeoil with the cascade of incandescent carbonaceous materials to distilloff a light fraction and thermally cracked heavier fractions,selectively withdrawing the fractions separately at different horizonsfrom the closed chamber, catalytically hydrogenating at least one of theso withdrawn fractions, fractionating the catalytically treated streamsto provide reforming streams, and recycling the reforming streams tocontact the cascade for thermal decomposition thereof.

13. A method of upgrading feedstock oil and distilling foreignhydrocarbon containing material carried thereby,

such as coal particles and foreign residua, the method comprising;providing a feedstock for the process including crude oil and foreignhydrocarbon containing material, contacting the feedstock with a cascadeof solid carbonaceous materials at a temperature sufficient to distillthe feedstock, the amount of carbonaceous materials being sufiicient toprovide sensible heat for such distill and for thermal cracking,providing an environment of hydrogen for such contacting, selectivelywithdrawing hydrogen entrained hydrocarbon vapors from a plurality ofdifferent horizons adjacent the place where the feedstock contacts thefalling cascade, and catalytically treating at least some of theso-withdrawn hydrogen entrained vapors.

14. A multivapor petrofiner comprising; a pressurized vertical vesselincluding a plurality of side inlets and offtakes for fluid streams,means for feeding a charge of at least initially carbonaceous solidmaterials under pressure into the pressurized vertical vessel, means forpreheating the charge of solid materials in an upper portion of thevertical vessel by combustion gases, means for accomplishing controlledpartial combustion of the initially carbonaceous materials to carbondioxide in oxygen in the vertical vessel below the upper preheatingportion, means for feeding the hot partially combusted solidcarbonaceous materials vertically downward as an annular cascade into anelongated gas isolated thermal treatment section of the vessel below thepartial combustion portion, a plurality of metered inlets into the gasisolated thermal treatment section for introducing fluid streamsthereinto at a plurality of horizon-s, means for causing the introducedstreams to intimately contact the falling hot annular cascade of solidmaterials, a plurality of metered ofitakes for withdrawing vapor streamproducts of the thermal treatment in the thermal treatment section,means for introducing a quenching gas into selected oiftakes, a pressurechange lock below the thermal treatment section in the vertical vessel,another section of the vertical vessel below the pressure change lockfor accomplishing further partial combustion of the solid materials, anda gas isolated section of the vessel below the last partial combustionsection including means for contacting an annular cascade of the hotsolids with a gas for cracking the same and removing the crackedproduct.

15. A multivapor petrofining method comprising; feeding a charge of atleast initially carbonaceous solid materials into a pressurized verticalvessel, accomplishing partial combustion on the solid materials to heatthe same, feeding the hot solid materials vertically downward in thevessel after the partial combustion through a thermal treating gasisolated zone of the vessel, providing a hydrogen environment in thethermal treating zone, intimately contacting for a controlled length oftime the falling hot solid materials, first with a gas such as ethane,butane, propane to thermally crack to ethylene, butadiene, propylene,then with at least one recycled reforming stream, then with an oilfeedstock including recycled bottoms and entrained finehydrocarbonaceous solids, rapidly removing the thermally treated fluidsin metered amounts at separate horizons in the thermal treating zone,rapidly quenching selected ones of the so removed streams,desulphurizing and catalytically reforming the removed streams ofthermally treated feedstock oil in an atmosphere of hydrogen,fractionating the catalytically treated streams to produce reformingfractions, and recycling the reforming fractions of the fractionatedstream to the thermal treating zone, reheating the solid carbonaceousmaterials in a separate isolated zone below the thermal treating zone byfurther partial combustion, contacting the reheated solid materials withmethane produced in the system for thermally cracking the methane, andrapidly quenching at least a portion of the so cracked methane to obtainacetylene.

(References on following page) References Cited by the Examiner UNITEDSTATES PATENTS Tuttle 208126 Tuttle 208--126 Schutt-e 208-126 5Kimberlin et a1 208-126 Weller 20s 143 18 2,834,658 5/1958 Lieifers eta1. 208167 2,910,427 10/1959 Cabbage 208-126 2,921,019 1/1960 Hart208167 DELBERT E. GANTZ, Primary Examiner.

PAUL M. COUGHLAN, ALPHONSO D. SULLIVAN,

Examiners.

1. A METHOD OF UPGRADING CRUDE OIL COMPRISING; CONTACTING CRUDE OIL WITHA FREE FALLING CASCADE OF SOLID CARBONACEOUS MATERIALS AT A TEMPERATURESUFFICIENT TO DISTILL CRUDE OIL AND IN SUFFICIENT AMOUNT TO PROVIDEADEQUATE SENSIBLE HEAT FOR DISTILLATION OF THE CRUDE OIL AND THERMALCRACKING THEREOF, INTRODUCING SAID CRUDE OIL IN CONTACT WITH THE FREEFALLING CASCADE OF SOLID CARBONACEOUS MATERIALS DURING THE FREE FALLTHEREOF, PROVIDING A HYDROGEN ENVIORNMENT FOR SAID CONTACTING,SELECTIVELY WITHDRAWING HYDROCARBON VAPORS FROM A PLURALITY OF DIFFERENTHORIZONS ADJACENT THE POINT OF CONTGACTING THE CRUDE OIL WITH THECASCADE SO THAT DIFFERENT AND MIXED VAPORS MAY BE WITHDRAWN FROM THEDIFFERNENT HORIZONS, AND CATALYTICALLY TREATING AT LEAST SOME OF THE SOWITHDRAWN HYDROGEN ENTRAINED VAPORS TO SATURATE WITH RESPECT TOHYDDROGEN AND TO REMOVE ORGANICALLY COMBINED OXYGEN,NITROGEN AND SULPHURAS RESPECTIVE HYDRIDES.